Pyrazoline compounds

ABSTRACT

Pyrazoline compounds of the formula (I): ##STR1## in which  EACH OF 
     B 1  to B 5  is hydrogen or C 1  to C 4  alkyl; 
     R 1  is hydrogen, alkyl or hydroxy; 
     R 2 , r 3 , r 5 , r 6  and R 7  independently of one another are hydrogen, chloro, bromo, fluoro, methyl, ethyl, methoxy or ethoxy; 
     R 4  is hydrogen, alkyl, benzyl, phenylethyl or also phenyl optionally bearing chloro, bromo, methyl, ethyl, methoxy, ethoxy, cyano, dialkylamino or SO 3  H as a substituent; 
     X is --O--, --S--, --NR 8  --, --NR 8  CO--, --NR 8  --SO 2  --, --OSO 3  -- or --SO 3  --; 
     R 8  is hydrogen, alkyl or alkyl bearing hydroxy or C 1  to C 4  alkoxy as a substituent; 
     A is hydrogen, sodium, potassium, unsubstituted or substituted ammonium, unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl; and 
     --NR 8  -- and A together may be an optionally quaternized saturated or unsaturated heterocyclic ring. 
     The compounds are eminently suitable as optical brighteners for example for acrylonitrile polymers, wool and polyamides.

This application is a division of Ser. No. 702,975 filed July 6, 1976, now issued as U.S. Pat. No. 4,129,563, on Dec. 12, 1978.

The invention relates to compounds of the general formula (I): ##STR2## in which B¹ to B⁵ are each hydrogen or C₁ to C₄ alkyl;

R¹ is hydrogen, alkyl or hydroxy;

R², r³, r⁵, r⁶ and R⁷ independently of one another are hydrogen, chloro, bromo, fluoro, methyl, ethyl, methoxy or ethoxy;

R⁴ is hydrogen, alkyl, benzyl, phenylethyl, phenyl or phenyl bearing chloro, bromo, methyl, ethyl, methoxy, ethoxy, cyano, dialkylamino or SO₃ H as a substituent;

X is --O--, --S--, --NR³ --, --NR⁸ CO--, --NR⁸ SO₂ --, --OSO₃ -- or --SO₃ --;

R⁸ is hydrogen, alkyl or alkyl bearing hydroxy or C₁ to C₄ alkoxy as a substituent;

A is hydrogen, sodium, potassium, ammonium, substituted ammonium or unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl; and

--NR⁸ -- and A together are an optionally quaternized saturated or unsaturated heterocyclic ring. Examples of dialkylaminophenyl radicals R⁴ are C₁ to C₄ dialkylaminophenyl such as dimethylaminophenyl, diethylaminophenyl or dibutylaminophenyl.

Examples of alkyl radicals R¹, R⁴ and R⁸ are those of one to six carbon atoms such as hexyl, amyl, butyl or propyl and particularly methyl or ethyl. Radicals R⁸ may also be β-hydroxyethyl, β-methoxyethyl, β-ethoxyethyl, β-propoxyethyl, β-butoxyethyl, β-methoxypropyl, β-ethoxypropyl, β-propoxypropyl or β-butoxypropyl. Examples of alkyl radicals B¹ to B⁵ are butyl, propyl, ethyl and methyl. B¹ to B⁵ are preferably hydrogen or methyl. Radicals A may be hydrogen or for example C₁ to C₁₃ alkyl which may be interrupted by oxygen or sulfur and may bear, as substituent, hydroxy, C₁ to C₄ alkoxy, phenoxy, cyano, chloro, bromo, carboxy, carbomethoxy, carboethoxy, carbobutoxy, carbamoyl, N-alkylcarbamoyl (alkyl being C₁ to C₆), SO₃ H, amino, C₁ to C₈ alkylamino or dialkylamino, pyrrolidino, piperidino, hexamethylene amino, morpholino, piperazino, N-methylpiperazino, N-β-hydroxyethylpiperazino, quaternary ammonium or cyclic ammonium. In one claimed embodiment R², R³, R⁴, R⁵, R⁶ and B³ are hydrogen. In another claimed embodiment R², R³, R⁴, R⁵, R⁶ and B³ are hydrogen and R⁷ is chlorine.

The following specific radicals A are given by way of example: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉, C₁₀ H₂₁ C₁₃ H₂₇, C₂ H₄ OH, C₃ H₆ OH, ##STR3## C₄ H₈ OH, C₆ H₁₂ OH, C₂ H₄ OC₂ H₄ OH, C₃ H₆ OC₂ H₄ OH, C₂ H₄ OCH₃, C₃ H₆ OCH₃, C₄ H₈ OCH₃, C₆ H₁₂ OCH₃, C₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₅, C₄ H₈ OC₂ H₅, C₂ H₄ OC₃ H₇, C₃ H₆ OC₃ H₇, C₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₉, C₃ H₆ OC₈ H₁₇, C₂ H₄ OC₆ H₅, C₃ H₆ OC₆ H₅, C₂ H₄ OC₂ H₄ OCH₃, C₂ H₄ OC₂ H₄ OC₂ H₅, C₂ H₄ OC₂ H₄ OC₄ H₉, C₂ H₄ OC₂ H₄ OC₆ H₅, C₂ H₄ (OC₂ H₄)₂ OCH₃, C₂ H₄ (OC₂ H₄)₂ OC₂ H₅, C₂ H₄ SCH₃, C₂ H₄ SC₂ H₅, C₂ H₄ SC₄ H₉, C₂ H₄ S--CH₂ --C₆ H₅, C₂ H₄ CN, C₅ H₁₀ CN, C₆ H₁₂ CN, C₇ H₁₄ CN, C₂ H₄ OC₂ H₄ CN, C₂ H₄ OC₂ H₄ CN, C₃ H₆ OC₂ H₄ CN, C₂ H₄ Cl, C₃ H₆ Cl, C₄ H₈ Cl, C₆ H₁₂ Cl, C₂ H₄ Br, C₃ H₆ Br, C₂ H₄ SO₃ H, CH₂ COOH, CH₂ --COOCH₃, C₂ H₄ COOH, C₂ H₄ COOC₂ H₅, C₂ H₄ COOC₄ H₉, C₂ H₄ CONHC₄ H₉, C₂ H₄ CONHCH₃, C₂ H₄ CONHC₂ H₅, C₂ H₄ CONHC₆ H₁₃, ##STR4## C₂ H₄ NH₂, C₂ H₄ NH--CH₃, C₃ H₆ NHC₂ H₅, C₃ H₆ NHC₃ H₇, C₂ H₄ NHC₄ H₉, ##STR5## C₃ H₆ NHC₆ H₁₃, C₃ H₆ NHC₈ H₁₇, C₂ H₄ N(CH₃)₂, C₂ H₄ N(C₂ H₅)₂, C₂ H₄ N(C₃ H₇)₂, C₂ H₄ N(C₄ H₉)₂, C₂ H₄ N(C₅ H₁₁)₂, C₂ H₄ N(C₆ H₁₃)₂, ##STR6##

Cycloalkyl, aralkyl or aryl radicals A are for example: ##STR7## Examples of radicals ##STR8## are: ##STR9##

Compounds of the formula (I) may be prepared by reacting a compound of the general formula (II): ##STR10## with a compound of the general formula (III):

    H--X--A                                                    (III)

in the presence of a base, X being --O--, --S--, --NR⁸ --, --NR⁸ CO--, --SO₃ -- or --NR⁸ SO₂ --.

Compounds of the formula (II) may be obtained by reacting a compound of the general formula (IV) or (V): ##STR11## B being Cl, Br or dialkylamino, with a compound of the general formula (VI): ##STR12##

Compounds of the formula (VI) are accessible in the following way: ##STR13## Compounds of the formula (VI)

Compounds of the formula (I) in which X--A is OSO₃ H may be obtained for example by reacting a compound of the general formula (I) in which X--A is OH with sulfuric acid.

Compounds of the formula (I) in which XA is SO₃ Na may be obtained from compounds of the formula (I) in which XA is OSO₃ Na or from (II) with an alkali metal sulfite, for example sodium sulfite.

Compounds of the formula (I) may also be prepared by the following method (B¹ to B⁵ being shown as hydrogen for the sake of simplicity): ##STR14## Compounds of the general formula (III)

Compounds of the general formula (I).

Compounds of the formula (I) may also be obtained by reacting a compound of the general formula (VIa): ##STR15## with a compound of the general formula (IV) or (V).

Compounds of the general formula (VIa) are accessible by the following method: ##STR16## Compounds of the general formula (VIa)

Compounds (I) in which R¹ is OH may be obtained from a compound of the general formula (VII): ##STR17## with a compound of the formula (III).

Compounds of the formula (VII) may be obtained by reacting a compound of the formula (VIII): ##STR18## with a compound of the formula (IV) or (V).

Compounds of the formula (VIII) are accessible as follows: ##STR19##

Compounds of the formula (VIII).

Compounds of the formula (I) in which R¹ is OH may also be obtained by reacting a compound of the formula (IX): ##STR20## with a compound of the formula (IV) or (V).

Compounds of the general formula (IX) may be obtained as follows: ##STR21##

Compounds of the general formula (IX).

Compounds of the formula (I) in which R¹ is OH may furthermore be obtained by the reaction of a compound of the formula (with B¹ to B⁵ represented as hydrogen for the sake of simplicity): ##STR22## or a precursor thereof of the formula: ##STR23## with a compound of the formula (III):

    H--X--A                                                    (III).

details concerning the reactions will be found in the Examples in which parts and percentages are by weight unless otherwise stated.

Particular industrial importance attaches to compounds of the general formula (Ia): ##STR24## in which R¹ is hydrogen or hydroxyl and XA has the meanings given above.

X is preferably --O--, --NR⁸ -- or --SO₃ -- and A is preferably hydrogen, sodium, potassium, C₁ to C₈ alkyl, an amino group bearing one or two C₁ to C₄ alkyl as substituents, alkyl bearing the said heterocyclic rings as substituents and radicals containing quaternary nitrogen.

Preferred radicals ##STR25## are: ##STR26##

The compounds of the general formula (I) are suitable as optical brighteners for cellulose esters and particularly for acrylonitrile polymers, wool and polyamides. Brilliant white effects are obtained having good fastness properties and particularly high degrees of whiteness. The compounds of the formula (I) are moreover suitable for use in detergents for brightening paper. The main method of application is liquor dyeing.

The production of precursors EXAMPLE A

(a) 80 parts of p-acetylaminobenzenesulfinic acid is dissolved with 44 parts of sodium bicarbonate in 400 parts of water. 76 parts of epichlorohydrin is dripped in at 45° to 50° C. and the whole is stirred for another two hours at 45° to 50° C. It is then allowed to cool, the pH of the solution is adjusted to 11.5 by adding 30 parts of 50% by weight caustic soda solution, and 85 parts (83.5% of theory) of 4-acetylaminophenyl-3'-hydroxypropene-2'-sulfone having a melting point of 165° to 170° C. is isolated by suction filtration. The molecular weight (calculated and found) is 255.

NMR (D-DMSO): 2.1(S), 4.2(M), 5.2(T), 6.65(brD), 6.95(brD), 7.8(S), 10.3(brS), 3:2:1:1:1:4:1.

(b) 63.7 parts of 4-acetylamino-3'-hydroxypropene-2'-sulfone is heated for an hour at 100° C. in a mixture of 90 parts of water and 90 parts of concentrated hydrochloric acid. After the whole has been cooled to 0° to 5° C. diazotization is carried out with a solution of 17.3 parts of sodium nitrite in 50 parts of water. The diazonium solution is dripped into a solution of 188 parts of sodium sulfite in 550 parts of water, stirred for one hour at ambient temperature, 100 parts of concentrated sulfuric acid is added, and the whole is heated for four hours at 100° C. After cooling the pH is adjusted to 10. The product is suction filtered and 41 parts (71.9% of theory) of 4-hydrazinophenyl-3'-hydroxypropene-2'-sulfone having a melting point of 136° to 142° C. is isolated.

(c) 11.4 parts of 4-hydrazinophenyl-3'-hydroxypropene-2'-sulfone and 10.15 parts of 4-chloro-β-chloropropiophenone are boiled under reflux in 50 parts of methyl glycol for two hours. The whole is cooled and 14 parts (74.5% of theory) of the compound of the formula: ##STR27## having a melting point of 224° to 228° C. is isolated by suction filtration. The compound has a pale yellow color (λ_(max). (dimethylformamide): 367 mm) and exhibits a blue fluorescence in solution.

The following compounds are prepared by the method described in Example A:

    __________________________________________________________________________      ##STR28##                                                                                               Fluoresecence in                                     Ex.                                                                               R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                           R.sup.5                                                                           R.sup.6                                                                            R.sup.7                                                                          m.pt.                                                                               dimethylformamide                                    __________________________________________________________________________     A.sup.1                                                                           H  H  H  H  3-Cl                                                                               Cl                                                                               222-229                                                                             greenish blue                                        A.sup.2                                                                           H  H  H  5-Cl                                                                              2-CH.sub.3                                                                         Cl                                                                               245-250                                                                             greenish blue                                        A.sup.3                                                                           H  H  CH.sub.3                                                                          H  H   Cl                                                                               218-226                                                                             blue                                                 A.sup.4                                                                           2-Cl                                                                              5-Cl                                                                              H  H  H   Cl                                                                               256-264                                                                             blue                                                 __________________________________________________________________________

EXAMPLE B

(a) 305 parts of p-acetylaminobenzenesulfinic acid is dissolved with 300 parts of sodium acetate in 1200 parts of water. 168 parts of epichlorohydrin is dripped in within two hours at 40° to 45° C. and the whole is stirred for another two hours at 40° to 45° C. The whole is allowed to cool and is suction filtered. The yield is 265 parts of 4-acetylaminophenyl-2'-hydroxy-3'-chloropropylsulfone having a melting point of 174° to 176° C. NMR (D-DMSO): 2.1(S), 3.45(D), 3.60(D), 4.1(M), 5.2(D), 7.82(S), 10.4(brS), 3:2:2:1:1:4:1--

(b) 58.4 parts of the compound from (a) is heated for one hour at 100° C. in 80 parts of water and 80 parts of concentrated hydrochloric acid. The whole is cooled and diazotized at 0° to 5° C. with a solution of 14.5 parts of sodium nitrite in 30 parts of water. Thirty minutes later the reaction mixture is poured into a solution of 150 parts of sodium sulfite in 250 parts of water and stirred for one hour at 10° to 15° C. After 70 parts of sulfuric acid has been added the whole is stirred for another hour at ambient temperature. The pH of the solution is then adjusted to 4.5 by dripping in 50% caustic soda solution; an oil thus separates and slowly crystallizes. The yield is 52 parts of 4-hydrazinophenyl-2'-hydroxy-3'-chloropropylsulfone having a melting point of 96° to 98° C. (after recrystallization from a mixture of ethyl acetate and cyclohexane).

(c) 66 parts of the compound from (b) and 51 parts of 4-chloro-β-chloropropiophenone are heated in 500 parts of ethyl alcohol for forty-five minutes at 75° to 78° C. The whole is then cooled and 75 parts of the compound of the formula: ##STR29## is isolated. It has a melting point of 157° to 158° C.

The following compounds are prepared by the method described in Example B:

    __________________________________________________________________________      ##STR30##                                                                                                Fluorescence                                        Ex.                                                                               R.sub.4                                                                          R.sub.5                                                                           R.sub.6                                                                           R.sub.7                                                                          B.sub.1                                                                           B.sub.2                                                                          B.sub.3                                                                           B.sub.4                                                                           B.sub.5                                                                           dimethylformamide                                   __________________________________________________________________________     B.sub.1                                                                           H H  3-Cl                                                                              Cl                                                                               H  H H  H  H  greenish blue                                       B.sub.2                                                                           H 5-Cl                                                                              2-CH.sub.3                                                                        Cl                                                                               H  H H  H  H  greenish blue                                       B.sub.3                                                                           H H  H  Cl                                                                               CH.sub.3                                                                          H H  H  H  blue                                                B.sub.4                                                                           H H  H  Cl                                                                               H  H H  CH.sub.3                                                                          H  blue                                                B.sub.5                                                                           H H  H  Cl                                                                               H  H CH.sub.3                                                                          H  H  blue                                                B.sub.6                                                                           H H  H  Cl                                                                               H  H H  CH.sub.3                                                                          CH.sub.3                                                                          blue                                                __________________________________________________________________________

EXAMPLE C

20.6 parts of the compound from Example B(c), 5 parts of sodium acetate and 5 parts of sodium iodide are heated in 300 parts of methyl ethyl ketone for ten hours at 60° to 65° C. The whole is cooled to ambient temperature and 400 parts of water and 400 parts of petroleum ether are added. 18 parts of the compound: ##STR31## having the melting point 154° to 156° C. (after recrystallization from toluene) is isolated by suction filtration.

The natural color of the compound is pale yellow; a solution of the compound in dimethylformamide has an intensely blue fluorescence.

The following compounds are prepared by the method described in Example C:

    ______________________________________                                          ##STR32##                                                                                                       Fluorescence in                              Ex.   R.sup.4 R.sup.5 R.sup.6                                                                               R.sup.7                                                                             dimethylformamide                            ______________________________________                                         C.sub.1                                                                              H       H       3-Cl   Cl   greenish blue                                C.sub.2                                                                              H       5-Cl    2-CH.sub.3                                                                            Cl   greenish blue                                C.sub.3                                                                              CH.sub.3                                                                               H       3-Cl   Cl   greenish blue                                ______________________________________                                    

EXAMPLE D

20.6 parts of the compound from Example B(c) and 10 parts of sodium acetate are heated in 30 parts of acetic anhydride for two hours at 100° C. The whole is allowed to cool and the product is hydrolyzed with 700 parts of water and suction filtered. 18 parts of the compound: ##STR33## is isolated; it has a melting point of 179° to 182° C. The compound is pale yellow in color; its solution in dimethylformamide has a greenish blue fluorescence.

EXAMPLE 1

12 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 25 parts of N,N-diethylethanolamine and 0.5 part of 50% caustic soda solution are stirred for thirty minutes at 60° to 80° C.

After the whole has cooled it is stirred into water and the product is suction filtered. 14 parts of a compound of the following constitution is obtained: ##STR34## It has a melting point of 143° to 147° C.

The reaction of 22 parts of p-allylsulfonylphenylhydrazine and 22 parts of p-ω-dichloropropiophenone in 250 parts of methanol results in 28 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline.

The compound melts at 212° to 213° C. after recrystallization from butanol. p-Allylsulfonylphenylhydrazine is obtained by the following method: 57 parts of p-allylsulfonylacetanilide is stirred with 130 parts of concentrated hydrochloric acid and 80 parts of water for two hours at refluxing temperature.

100 parts of ice is added and diazotization is carried out at 0° to 5° C. with 18 parts of sodium nitrite dissolved in 40 parts of water. The diazonium salt solution is allowed to flow at 0° to 8° C. into a solution of 100 parts of sodium sulfite and 400 parts of water and stirring is continued for another hour. The solution is made acid with 170 parts of sulfuric acid and stirred for another four hours at 90° to 95° C. After the whole has been cooled and the pH adjusted to 8 to 9 40 parts of p-allylsulfonylphenylhydrazine is precipitated. After the hydrazine has been recrystallized from toluene it has a melting point of 90° to 91° C.

p-Allylsulfonylacetanilide may be prepared as follows:

50 parts of p-acetylaminophenylsulfinic acid and 25 parts of sodium hydrogen carbonate are suspended in 300 parts of water. While stirring intensely 36 parts of allyl bromide is dripped in within three hours at 50° to 60° C. Stirring is continued for another four hours at 60° C. 45 parts of p-allylsulfonylacetanilide is obtained with a melting point of 116° to 118° C.

EXAMPLE 2

13 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 25 parts of morpholine and 0.5 part of 50% caustic soda solution are stirred for three hours at 80° to 90° C. After the whole has been cooled it is stirred into 200 parts of ice. 15.5 parts of the following compound is obtained: ##STR35## It has a melting point of 155° to 162° C.

EXAMPLE 3

12 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 25 parts of N-methylpiperazine are stirred for one hour at 100° C. When cold the whole is poured onto ice. 13 parts of the compound of the following constitution: ##STR36## is obtained. After having been stirred with petroleum ether the amorphous compound melts at 45° to 55° C.

EXAMPLE 4

10 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 25 parts of N-2-aminobutylpiperidine are stirred for six hours at 100° C. After the whole has been cooled it is stirred into 200 parts of ice. The oily residue is dried and then stirred with petroleum ether. 12 parts of an amorphous compound is obtained having a melting point of 70° to 82° C. and the following structure: ##STR37##

EXAMPLE 5

10 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 25 parts of butylamine are stirred for five hours at 80° C. After the whole has been cooled it is stirred into 150 parts of ice. 12 parts of the following compound is obtained: ##STR38## It has a melting point of 112° to 114° C.

EXAMPLE 6

The following compound: ##STR39## is obtained analogously to Example 5 with dimethylaminopropylamine. After the compound has been recrystallized from methylcyclohexane it melts at 102° to 103° C.

EXAMPLE 7

12 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 25 parts of N,N-dimethylpropanolamine and 1 part of 30% caustic potash solution are stirred for fifteen minutes at 70° to 80° C. After the whole has cooled it is stirred into water and suction filtered. 14 parts of the following compound is obtained: ##STR40## It has a melting point of 138° to 139° C.

EXAMPLE 8

The reaction according to Example 7 is carried out in N,N-dimethylethanolamine. The following compound is obtained in a quantitative yield: ##STR41## It has a melting point of from 150° to 151° C.

EXAMPLE 9

12 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 30 parts of N-methylpyrrolidone, 10 parts of water and 1 part of 50% caustic soda solution are stirred for sixty minutes at 80° to 90° C. The whole is cooled and made acid and then stirred into ice. 12 parts of a compound of the following constitution is obtained. ##STR42## It has a melting point of 160° to 162° C.

EXAMPLE 10

10 parts of the compound from Example 9 is stirred at ambient temperature into 60 parts of concentrated sulfuric acid. The whole is stirred for another twenty hours and poured onto ice. The precipitated product of the following constitution is isolated: ##STR43##

EXAMPLE 11

5 parts of 1-p-(methallylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 30 parts of ethanolamine are stirred for four hours at 120° C. After cooling the product is precipitated with water and suction filtered. 5 parts of the following compound is obtained: ##STR44## It has a melting point of 178° to 179° C.

1-p-(methallylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline is obtained by the reaction of p-methallylsulfonylphenylhydrazine with 4,ω-dichloropropiophenone in methanol. It has a melting point of 180° to 182° C.

p-Methallylsulfonylphenylhydrazine is obtained as follows: p-methallylsulfonylacetanilide is converted into the aniline derivative. Diazotization and reduction with sodium sulfite gives p-methallylsulfonylphenylhydrazine in a yield of 80 to 85% of theory. The melting point is 95° to 98° C.

EXAMPLE 12

5 parts of 1-p-(allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 30 parts of diethanolamine are stirred for three hours at 120° C. After the whole has been cooled the product is precipitated with water and suction filtered. 5.3 parts of the following compound is obtained: ##STR45## It has a melting point of 72° to 74° C.

EXAMPLE 13

10 parts of 1-(p-crotylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 20 parts of diethylethanolamine and 1 part of 30% caustic soda solution are stirred for forty-five minutes at 70° to 80° C.

After the whole has been cooled it is stirred into water and suction filtered. 11 parts of a compound of the following constitution is obtained: ##STR46##

1-(p-crotylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline is obtained by the reaction of p-crotylsulfonylphenylhydrazine with p-ω-dichloropropiophenone in methanol. The compound melts at 123° to 124° C. after it has been recrystallized from isobutanol.

p-Crotylsulfonylphenylhydrazine is obtained as follows: p-crotylsulfonylacetanilide is converted into the aniline derivative. Diazotization and reduction with sodium sulfite gives p-crotylsulfonylphenylhydrazine in a yield of 75 to 80% of theory. The melting point is 115° to 116° C.

EXAMPLE 14

10 parts of 1-(p-crotylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 20 parts of N,N-dimethylpropanolamine and 1 part of saturated sodium carbonate solution are stirred for sixty minutes at 90° C. 11 parts of the following compound is obtained: ##STR47##

EXAMPLE 15

10 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 20 parts of 2-ethylhexyl alcohol and 1 part of 50% caustic soda solution are stirred at 80° C. for thirty minutes. The following compound is obtained in a quantitative yield: ##STR48## It has a melting point of 152° to 155° C.

EXAMPLE 16

10 parts of 1-(p-allylsulfonylphenyl)-Δ² -pyrazoline, 20 parts of ethyl glycol and 1 part of 50% caustic soda solution are stirred for forty-five minutes at 80° C. 12 parts of the following compound is obtained: ##STR49## It has a melting point of 102° to 104° C.

EXAMPLE 17

The reaction described in Example 16 is carried out with methyl diglycol. 13 parts of the following compound is obtained: ##STR50## It has a melting point of 176° to 177° C.

EXAMPLE 18

10.8 parts of 1-(p-allylsulfonyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 20 parts of N-methylpyrrolidone, 30 parts of water, 7.5 parts of taurine and 5.3 parts of 50% caustic soda solution are stirred for about thirty minutes at 90° C. until a sample has good solubility in water. 11 parts of the following compound crystallizes out in the neutral region: ##STR51## It has a melting point of 245° to 248° C.

EXAMPLE 19

10 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 6 parts of acetamide and 0.5 part of sodium methylate are heated to 100° C. Twenty minutes later the melt is allowed to cool and crystallized from glacial acetic acid. 8 parts of the following compound is obtained: ##STR52## It has a melting point of 198° to 199° C.

EXAMPLE 20

10 parts of the compound from Example 7 is dissolved in 30 parts of toluene. While stirring 4 parts of dimethyl sulfate is dripped in at 80° C. 12 parts of product of the following constitution is isolated as an oil: ##STR53##

EXAMPLE 21

12 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline, 25 parts of N-hydroxyethylmorpholine and 1 part of 30% caustic soda solution are stirred for twenty-five minutes at 70° to 80° C. The product is stirred into water. 14 parts of the following compound is obtained: ##STR54## It has a melting point of 144° to 145° C.

EXAMPLE 22

10 parts of the compound from Example 21 is dissolved in 30 parts of toluene. While stirring 4 parts of methyl iodide is dripped in at 100° C. and the whole is stirred for another four hours. 12 parts of the following compound is isolated as an amorphous product: ##STR55##

EXAMPLE 23

10 parts of 1-(p-allylsulfonylphenyl)-3-(p-chlorophenyl)-Δ² -pyrazoline and 25 parts of 2-ethylhexylamine are stirred for five hours at refluxing temperature. The product is stirred into water. 12 parts of the following compound is obtained: ##STR56## It has a melting point of 74° to 75° C.

EXAMPLE 24

The 2-ethylhexylamine used in Example 23 is replaced by piperidine. The following compound is obtained in a quantitative yield: ##STR57## It has a melting point of 164° to 165° C.

EXAMPLE 25

The 2-ethylhexylamine is Example 23 is replaced by hexamethyleneimine. A quantitative yield of the following compound is obtained: ##STR58## It has a melting point of 79° to 80° C.

The following compounds may be prepared according to the Examples given:

                                      Table I                                      __________________________________________________________________________      ##STR59##                                                                                                            Shade of                                Ex.                                                                               R.sup.1                                                                           XA                    Dissolved in                                                                              fluorescence                            __________________________________________________________________________      26                                                                               H  OCH.sub.3             dimethylformamide                                                                         violet                                   27                                                                               H  OC.sub.2 H.sub.5      "          "                                        28                                                                               H  OC.sub.3 H.sub.7      "          "                                        29                                                                               H  OC.sub.6 H.sub.13     "          "                                        30                                                                               H  OC.sub.8 H.sub.17     "          "                                        31                                                                               H  OC.sub.10 H.sub.21    "          "                                        32                                                                               H  OC.sub.2 H.sub.4 OH   "          "                                        33                                                                               H                                                                                  ##STR60##                                                                34                                                                               H  OC.sub.6 H.sub.12 OH  "          "                                        35                                                                               H  OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                                                                 "          "                                        36                                                                               H  OC.sub.2 H.sub.4 OCH.sub.3                                                                           "          "                                        37                                                                               H  OC.sub.2 H.sub.4 OC.sub.4 H.sub.9                                                                    "          "                                        38                                                                               H  OC.sub.3 H.sub.6 OC.sub.8 H.sub.17                                                                   "          "                                        39                                                                               H  OC.sub.2 H.sub.4 (OC.sub.2 H.sub.4).sub.2 OCH.sub.3                                                  "          "                                        40                                                                               H  OC.sub.2 H.sub.4 SCH.sub.3                                                                           "          "                                        41                                                                               H  OC.sub.2 H.sub.4 SC.sub.6 H.sub.5                                                                    "          "                                        42                                                                               H  OC.sub.2 H.sub.4 CN   "          "                                        43                                                                               H  OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 CN                                                                 "          "                                        44                                                                               H  OC.sub.2 H.sub.4 Cl   "          "                                        45                                                                               H  OC.sub.4 H.sub.8 Cl   "          "                                        46                                                                               H  OC.sub.6 H.sub.12 Cl  "          "                                        47                                                                               H  OC.sub.3 H.sub.6 Br   "          "                                        48                                                                               H  OC.sub.2 H.sub.4 COOH dilute alkali                                                                             bluish violet                            49                                                                               H  OC.sub.2 H.sub.4 COOCH.sub.3                                                                         dimethylformamide                                                                         violet                                   50                                                                               H  OC.sub.2 H.sub.4 N(C.sub.3 H.sub.7).sub.2                                                            dilute acid                                                                               bluish violet                            51                                                                               H  OC.sub.2 H.sub.4 N(C.sub.4 H.sub.9).sub.2                                                            "          "                                        52                                                                               H                                                                                  ##STR61##            "          "                                        53                                                                               H                                                                                  ##STR62##            "          "                                        54                                                                               H                                                                                  ##STR63##            "          "                                        55                                                                               H  OC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2                                                            "          "                                        56                                                                               H  OC.sub.3 H.sub.6 N(C.sub.3 H.sub.7).sub.2                                                            "          "                                        57                                                                               H  OC.sub.3 H.sub.6 N(C.sub.4 H.sub.9).sub.2                                                            "          "                                        58                                                                               H                                                                                  ##STR64##                                                                59                                                                               H                                                                                  ##STR65##            "          "                                        60                                                                               H  OC.sub.4 H.sub.8N(CH.sub.3).sub.2                                                                    "          "                                        61                                                                               H  OC.sub.4 H.sub.8N(C.sub.2 H.sub.5).sub.2                                                             "          "                                        62                                                                               H  OC.sub.4 H.sub.8N(C.sub.3 H.sub.7).sub.2                                                             "          "                                        63                                                                               H                                                                                  ##STR66##            "          "                                        64                                                                               H                                                                                  ##STR67##            "          "                                        65                                                                               H  OC.sub.6 H.sub.12N(CH.sub.3).sub.2                                                                   "          "                                        66                                                                               H  OC.sub.6 H.sub.12N(C.sub.2 H.sub.5).sub.2                                                            "          "                                        67                                                                               H  OC.sub.6 H.sub.12 N(C.sub.4 H.sub.9).sub.2                                                           "          "                                        68                                                                               H                                                                                  ##STR68##            "          "                                        69                                                                               H                                                                                  ##STR69##            "          "                                        70                                                                               H                                                                                  ##STR70##            "          "                                        71                                                                               H                                                                                  ##STR71##            "          "                                        72                                                                               H                                                                                  ##STR72##            "          "                                        73                                                                               H                                                                                  ##STR73##            "          "                                        74                                                                               H                                                                                  ##STR74##            "          "                                        75                                                                               H                                                                                  ##STR75##            "          "                                        76                                                                               H                                                                                  ##STR76##            "          "                                        77                                                                               H                                                                                  ##STR77##            "          "                                        78                                                                               H                                                                                  ##STR78##            "          "                                        79                                                                               H                                                                                  ##STR79##            "          "                                        80                                                                               H                                                                                  ##STR80##            "          "                                        81                                                                               H                                                                                  ##STR81##            "          "                                        82                                                                               H                                                                                  ##STR82##            "          "                                        83                                                                               H                                                                                  ##STR83##            "          "                                        84                                                                               H                                                                                  ##STR84##            "          "                                        85                                                                               H                                                                                  ##STR85##            "          "                                        86                                                                               H                                                                                  ##STR86##            "          "                                        87                                                                               H                                                                                  ##STR87##            "          "                                        88                                                                               H                                                                                  ##STR88##            "          "                                        89                                                                               H                                                                                  ##STR89##            "          "                                        90                                                                               H                                                                                  ##STR90##            "          "                                        91                                                                               H                                                                                  ##STR91##            "          "                                        92                                                                               H                                                                                  ##STR92##            "          "                                        93                                                                               H                                                                                  ##STR93##            "          "                                        94                                                                               H                                                                                  ##STR94##            "          "                                        95                                                                               H                                                                                  ##STR95##            "          "                                        96                                                                               H                                                                                  ##STR96##            "          "                                        97                                                                               H                                                                                  ##STR97##            dimethylformamide                                                                         violet                                   98                                                                               H                                                                                  ##STR98##            "          "                                        99                                                                               H                                                                                  ##STR99##            "          "                                        100                                                                              H                                                                                  ##STR100##           "          "                                        101                                                                              H                                                                                  ##STR101##           "          "                                       102                                                                               H  OC.sub.2 H.sub.4 .sup.⊕N(CH.sub.3).sub.3 CH.sub.3 SO.sub.4.sup..           crclbar.              water      bluish violet                           103                                                                               H                                                                                  ##STR102##           "          "                                       104                                                                               H                                                                                  ##STR103##           "          "                                       105                                                                               H                                                                                  ##STR104##           "          "                                       106                                                                               H  OC.sub.3 H.sub.6.sup.⊕N(CH.sub.3).sub.3 CH.sub.3 SO.sub.4.sup..c           rclbar.               "          "                                       107                                                                               H                                                                                  ##STR105##           "          "                                       108                                                                               H                                                                                  ##STR106##           "          "                                       109                                                                               H                                                                                  ##STR107##           "          "                                       110                                                                               H  OC.sub.4 H.sub.8  .sup.⊕N(CH.sub.3).sub.3 CH.sub.3 SO.sub.4.sup.           ⊖             "          "                                       111                                                                               H                                                                                  ##STR108##           "          "                                       112                                                                               H  OC.sub.6 H.sub.12 .sup.⊕N(CH.sub.3).sub.3 CH.sub.3 SO.sub.4.sup.           ⊖             "          "                                       113                                                                               H                                                                                  ##STR109##           "          "                                       114                                                                               H                                                                                  ##STR110##           "          "                                       115                                                                               H                                                                                  ##STR111##           "          "                                       116                                                                               H                                                                                  ##STR112##           "          "                                       117                                                                               H                                                                                  ##STR113##           "          "                                       118                                                                               H                                                                                  ##STR114##           "          "                                       119                                                                               H                                                                                  ##STR115##           "          "                                       120                                                                               H                                                                                  ##STR116##           "          "                                       121                                                                               H                                                                                  ##STR117##           "          "                                       122                                                                               H                                                                                  ##STR118##           "          "                                       123                                                                               H                                                                                  ##STR119##           "          "                                       124                                                                               H                                                                                  ##STR120##           "          "                                       125                                                                               H                                                                                  ##STR121##           "          "                                       126                                                                               H                                                                                  ##STR122##           "          "                                       127                                                                               H                                                                                  ##STR123##           "          "                                       128                                                                               H                                                                                  ##STR124##           "          "                                       129                                                                               H                                                                                  ##STR125##           "          "                                       130                                                                               H                                                                                  ##STR126##           "          "                                       131                                                                               H                                                                                  ##STR127##           "          "                                       132                                                                               H                                                                                  ##STR128##           "          "                                       133                                                                               H                                                                                  ##STR129##           dimethylformamide                                                                         violet                                  134                                                                               H                                                                                  ##STR130##           "          "                                       135                                                                               H  OCH.sub.2C.sub.6 H.sub.5                                                                             "          "                                       136                                                                               H  OCH.sub.2C.sub.6 H.sub.4 SO.sub.3 H                                                                  dilute alkali                                                                             bluish violet                           137                                                                               H  OC.sub.2 H.sub.4 C.sub.6 H.sub.4 SO.sub.3 H                                                          "          "                                       138                                                                               H  OC.sub.6 H.sub.4 SO.sub.3 H                                                                          "          "                                       139                                                                               H  OC.sub.6 H.sub.3 (SO.sub.3 H).sub.2                                                                  "          "                                       140                                                                               H  OC.sub.2 H.sub.4 C.sub.6 H.sub.5                                                                     dimethylformamide                                                                         violet                                  141                                                                               H  OC.sub.6 H.sub.4 CH.sub.3                                                                            "          "                                       142                                                                               H  OC.sub.2 H.sub.4C.sub.6 H.sub.4 CH.sub.3                                                             "          "                                       143                                                                               H  OC.sub.6 H.sub.5      "          "                                       144                                                                               H  OC.sub.6 H.sub.5 OC.sub.2 H.sub.5                                                                    "          "                                       145                                                                               H  NHCH.sub.3            "          "                                       146                                                                               H  NHC.sub.2 H.sub.5     "          "                                       147                                                                               H  NHC.sub.3 H.sub.7     "          "                                       148                                                                               H  NHC.sub.5 H.sub.11    "          "                                       149                                                                               H  NHC.sub. 6 H.sub.13   "          "                                       150                                                                               H  NHC.sub.7 H.sub.15    "          bluish violet                           151                                                                               H  NHC.sub.8 H.sub.17    "          "                                       152                                                                               H  NHC.sub.9 H.sub.19    "          "                                       153                                                                               H  NHC.sub.10 H.sub.21   "          "                                       154                                                                               H  NHC.sub.13 H.sub.27   "          "                                       155                                                                               H  NHC.sub.2 H.sub.4 OH  "          "                                       156                                                                               H  NHC.sub.3 H.sub.6 OH  "          "                                       157                                                                               H  NHC.sub.6 H.sub.12 OH "          "                                       158                                                                               H  NHC.sub.2 H.sub.4 OCH.sub.3                                                                          "          "                                       159                                                                               H  NHC.sub.3 H.sub.6 OCH.sub.3                                                                          "          "                                       160                                                                               H  NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                                   "          "                                       161                                                                               H  NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                                   "          "                                       162                                                                               H  NHC.sub.2 H.sub.4 OC.sub.8 H.sub.17                                                                  "          "                                       163                                                                               H  NHC.sub.3 H.sub.6 OC.sub.8 H.sub.17                                                                  "          "                                       164                                                                               H  NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                                  "          "                                       165                                                                               H  NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub. 3                                                        "          "                                       166                                                                               H  NHC.sub.2 H.sub.4 CN  "          "                                       167                                                                               H  NHC.sub.5 H.sub.10 CN "          "                                       168                                                                               H  NHC.sub.6 H.sub.12 CN "          "                                       169                                                                               H  NHC.sub.2 H.sub.4 COOH                                                                               dilute alkali                                                                             blue                                    170                                                                               H  NHC.sub.2 H.sub.4 COOCH.sub.3                                                                        dimethylformamide                                                                         bluish violet                           171                                                                               H  NHC.sub.2 H.sub.4 COOC.sub.4 H.sub.9                                                                 "          "                                       172                                                                               H  NHC.sub.2 H.sub.4 CONH.sub.2                                                                         "          "                                       173                                                                               H  NHC.sub.2 H.sub.4 CONHC.sub.2 H.sub.5                                                                "          "                                       174                                                                               H  NHC.sub.2 H.sub.4 CONHC.sub.6 H.sub.13                                                               "          "                                       175                                                                               H                                                                                  ##STR131##           "          "                                       176                                                                               H                                                                                  ##STR132##           "          "                                       177                                                                               H  NHC.sub.2 H.sub.4NHC.sub.2 H.sub.5                                                                   dilute acid                                                                               blue                                    178                                                                               H  NHC.sub.2 H.sub.4NHC.sub.3 H.sub.7                                                                   "          "                                       179                                                                               H                                                                                  ##STR133##           "          "                                       180                                                                               H                                                                                  ##STR134##           "          "                                       181                                                                               H                                                                                  ##STR135##           "          "                                       182                                                                               H                                                                                  ##STR136##           "          "                                       183                                                                               H                                                                                  ##STR137##           "          "                                       184                                                                               H                                                                                  ##STR138##           "          "                                       185                                                                               H                                                                                  ##STR139##           "          "                                       186                                                                               H                                                                                  ##STR140##           "          "                                       187                                                                               H                                                                                  ##STR141##           "          "                                       188                                                                               H                                                                                  ##STR142##           "          "                                       189                                                                               H                                                                                  ##STR143##           "          "                                       190                                                                               H                                                                                  ##STR144##           "          "                                       191                                                                               H                                                                                  ##STR145##           "          "                                       192                                                                               H                                                                                  ##STR146##           "          "                                       193                                                                               H                                                                                  ##STR147##           "          "                                       194                                                                               H                                                                                  ##STR148##           "          "                                       195                                                                               H                                                                                  ##STR149##           "          "                                       196                                                                               H                                                                                  ##STR150##           "          "                                       197                                                                               H                                                                                  ##STR151##           "          "                                       198                                                                               H                                                                                  ##STR152##           "          "                                       199                                                                               H                                                                                  ##STR153##           "          "                                       200                                                                               H                                                                                  ##STR154##           "          "                                       201                                                                               H                                                                                  ##STR155##           "          "                                       202                                                                               H                                                                                  ##STR156##           "          "                                       203                                                                               H                                                                                  ##STR157##           "          "                                       204                                                                               H                                                                                  ##STR158##           "          "                                       205                                                                               H                                                                                  ##STR159##           "          "                                       206                                                                               H                                                                                  ##STR160##           "          "                                       207                                                                               H                                                                                  ##STR161##           "          "                                       208                                                                               H                                                                                  ##STR162##           "          "                                       209                                                                               H                                                                                  ##STR163##           "          "                                       210                                                                               H                                                                                  ##STR164##           "          "                                       211                                                                               H                                                                                  ##STR165##           "          "                                       212                                                                               H                                                                                  ##STR166##           "          "                                       213                                                                               H                                                                                  ##STR167##           "          "                                       214                                                                               H                                                                                  ##STR168##           "          "                                       215                                                                               H                                                                                  ##STR169##           "          "                                       216                                                                               H                                                                                  ##STR170##           "          "                                       217                                                                               H                                                                                  ##STR171##           "          "                                       218                                                                               H                                                                                  ##STR172##           "          "                                       219                                                                               H                                                                                  ##STR173##           "          "                                       220                                                                               H                                                                                  ##STR174##           "          "                                       221                                                                               H                                                                                  ##STR175##           "          "                                       222                                                                               H                                                                                  ##STR176##           "          "                                       223                                                                               H                                                                                  ##STR177##           "          "                                       224                                                                               H                                                                                  ##STR178##           "          "                                       225                                                                               H                                                                                  ##STR179##           "          "                                       226                                                                               H                                                                                  ##STR180##           "          "                                       227                                                                               H                                                                                  ##STR181##           water      "                                       228                                                                               H                                                                                  ##STR182##           "          "                                       229                                                                               H                                                                                  ##STR183##           "          "                                       230                                                                               H                                                                                  ##STR184##           "          "                                       231                                                                               H                                                                                  ##STR185##           "          "                                       232                                                                               H                                                                                  ##STR186##           "          "                                       233                                                                               H                                                                                  ##STR187##           "          "                                       234                                                                               H                                                                                  ##STR188##           "          "                                       235                                                                               H                                                                                  ##STR189##           "          "                                       236                                                                               H                                                                                  ##STR190##           "          "                                       237                                                                               H                                                                                  ##STR191##           "          "                                       238                                                                               H                                                                                  ##STR192##           "          "                                       239                                                                               H                                                                                  ##STR193##           "          "                                       240                                                                               H                                                                                  ##STR194##           "          "                                       241                                                                               H                                                                                  ##STR195##           "          "                                       242                                                                               H                                                                                  ##STR196##           dimethylformamide                                                                         bluish violet                           243                                                                               C.sub.2 H.sub.5                                                                    ##STR197##           "          "                                       244                                                                               C.sub.2 H.sub.5                                                                    ##STR198##           "          "                                       245                                                                               H                                                                                  ##STR199##           "          "                                       246                                                                               H                                                                                  ##STR200##           "          "                                       247                                                                               H                                                                                  ##STR201##           "          "                                       248                                                                               H                                                                                  ##STR202##           "          "                                       249                                                                               H                                                                                  ##STR203##           "          "                                       250                                                                               H                                                                                  ##STR204##           "          "                                       251                                                                               H                                                                                  ##STR205##           "          "                                       252                                                                               H                                                                                  ##STR206##           water      blue                                    253                                                                               H                                                                                  ##STR207##           "          "                                       254                                                                               CH.sub.3                                                                          OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                   dilute acid                                                                               bluish violet                           255                                                                               "  OC.sub.2 H.sub.4 N(C.sub.3 H.sub.7).sub.2                                                            "          "                                       256                                                                               CH.sub.3                                                                          OC.sub.3 H.sub.6 N(C.sub. 2 H.sub.5).sub.2                                                           "          "                                       257                                                                               CH.sub.3                                                                          OC.sub.2 H.sub.4 N(C.sub.4 H.sub.9).sub.2                                                            "          "                                       258                                                                               CH.sub.3                                                                           ##STR208##           "          "                                       259                                                                               CH.sub.3                                                                           ##STR209##           "          "                                       260                                                                               CH.sub.3                                                                           ##STR210##           "          "                                       261                                                                               CH.sub.3                                                                           ##STR211##           "          "                                       262                                                                               CH.sub.3                                                                           ##STR212##           "          "                                       263                                                                               C.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                   "          "                                       264                                                                               C.sub.2 H.sub.5                                                                   OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                                   "          "                                       265                                                                               C.sub.3 H.sub.6                                                                   OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                   "          "                                       266                                                                               C.sub.3 H.sub.6                                                                   OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                                   "          "                                       267                                                                               CH.sub.3                                                                           ##STR213##           "          "                                       268                                                                               CH.sub.3                                                                          N(CH.sub.3).sub.2     dimethylformamide                                                                         violet                                  269                                                                               CH.sub.3                                                                          N(C.sub.2 H.sub.5).sub.2                                                                             "          "                                       270                                                                               CH.sub.3                                                                          N(C.sub.4 H.sub.9).sub.2                                                                             "          "                                       271                                                                               CH.sub.3                                                                           ##STR214##           "          "                                       272                                                                               CH.sub.3                                                                           ##STR215##           "          "                                       273                                                                               CH.sub.3                                                                           ##STR216##           "          "                                       274                                                                               CH.sub.3                                                                           ##STR217##           "          "                                       275                                                                               CH.sub.3                                                                           ##STR218##           "          "                                       276                                                                               CH.sub.3                                                                          NHC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                  dilute acid                                                                               bluish violet                           277                                                                               CH.sub.3                                                                          NHC.sub.3 H.sub.6N(C.sub.2 H.sub.5).sub.2                                                            "          "                                       278                                                                               CH.sub.3                                                                          NHC.sub.3 H.sub.6N(C.sub.4 H.sub.9).sub.2                                                            "          "                                       279                                                                               CH.sub.3                                                                           ##STR219##           "          "                                       280                                                                               CH.sub.3                                                                           ##STR220##           "          "                                       281                                                                               CH.sub.3                                                                           ##STR221##           "          "                                       282                                                                               CH.sub.3                                                                           ##STR222##           "          "                                       283                                                                               H  SCH.sub.3             dimethylformamide                                                                         violet                                  284                                                                               H  SC.sub.2 H.sub.5      "          "                                       285                                                                               H  SC.sub.4 H.sub.9      "          "                                       286                                                                               CH.sub.3                                                                          SCH.sub.2CHCH.sub.2   "          "                                       287                                                                               C.sub.2 H.sub.5                                                                   SCH.sub.2C.sub.6 H.sub.5                                                                             "          "                                       288                                                                               H  SCH.sub.2 COOH        dilute alkali                                                                             blue                                    289                                                                               H  SC.sub.2 H.sub.4 COOH "          "                                       290                                                                               CH.sub.3                                                                          SC.sub.2 H.sub.4 COOH "          "                                       291                                                                               CH.sub.3                                                                           ##STR223##           "          "                                       292                                                                               C.sub.2 H.sub.5                                                                    ##STR224##           "          "                                       293                                                                               CH.sub.3                                                                           ##STR225##           "          "                                       294                                                                               CH.sub.3                                                                           ##STR226##           "          "                                       295                                                                               CH.sub.3                                                                          OH                    dimethylformamide                                                                         bluish violet                           296                                                                               CH.sub.3                                                                           ##STR227##           dilute alkali                                                                             blue                                    297                                                                               CH.sub.3                                                                          NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                                       "          "                                       298                                                                               CH.sub.3                                                                          OCH.sub.2 CH.sub.2 SO.sub.3 H                                                                        "          "                                       299                                                                               H  OCH.sub.2 CH.sub.2 SO.sub.3 H                                                                        "          "                                       300                                                                               H                                                                                  ##STR228##           "          "                                       301                                                                               H                                                                                  ##STR229##           dimethylformamide                                                                         violet                                  302                                                                               H                                                                                  ##STR230##           "          "                                       303                                                                               H                                                                                  ##STR231##           "          "                                       304                                                                               H                                                                                  ##STR232##           "          "                                       305                                                                               H                                                                                  ##STR233##           "          "                                       306                                                                               H                                                                                  ##STR234##           "          "                                       307                                                                               H  NHSO.sub.2C.sub.6 H.sub.5                                                                            "          "                                       308                                                                               H                                                                                  ##STR235##           "          "                                       309                                                                               H                                                                                  ##STR236##           "          "                                       310                                                                               H                                                                                  ##STR237##           "          "                                       311                                                                               CH.sub.3                                                                           ##STR238##           "          "                                       312                                                                               CH.sub.3                                                                           ##STR239##           "          "                                       313                                                                               CH.sub.3                                                                           ##STR240##           "          "                                       314                                                                               CH.sub.3                                                                           ##STR241##           "          "                                       315                                                                               CH.sub.3                                                                           ##STR242##           "          "                                       __________________________________________________________________________

example 316

12 parts of 1-(p-allylsulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline, 25 parts of N,N-diethylethanolamine and 0.5 part of 30% caustic soda solution are stirred for thirty minutes at 70° to 80° C.

After the whole has been cooled it is stirred into water and suction filtered. 15 parts of a compound of the following constitution is obtained: ##STR243## The melting point is 154° to 155° C.

The reaction of 22 parts of p-allylsulfonylphenylhydrazine and 23 parts of 3,4-ω-trichloropropiophenone on 250 parts of methanol gives 29 parts of 1-(p-allylsulfonylphenyl)-3-(3,4-dichlorophenyl)-Δ² -pyrazoline. The melting point is 184° to 186° C.

EXAMPLE 317

10 parts of 1-(p-crotylsulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline and 25 parts of N,N-dimethylpropanolamine are heated to 90° to 100° C. 1 part of 50% caustic soda solution is added in three portions over a period of thirty minutes. The whole is stirred for another thirty minutes, allowed to cool, stirred into water and suction filtered. 12 parts of the following compound is obtained: ##STR244##

The 1-(p-crotylsulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline is obtained as follows:

14 parts of p-crotylsulfonylphenylhydrazine, 12 parts of 3,4-ω-trichloropropiophenone and 150 parts of methanol are stirred for four hours at 65° C. 18 parts of 1-(p-crotyl-sulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline crystallizes out overnight. The melting point is 170° to 171° C.

EXAMPLE 318

12 parts of 1-(p-allylsulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline and 20 parts of hexamethyleneimine are stirred for six hours at 100° C. The excess hexamethyleneimine is distilled off at subatmospheric pressure and the residue is taken up in methanol. 14 parts of the following compound is obtained: ##STR245## The melting point is 144° to 145° C.

EXAMPLE 319

12 parts of 1-(p-allylsulfonylphenyl)-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline and 25 parts of methoxypropylamine are heated to 100° C. 0.3 part of 40% caustic potash solution is added and stirring is continued for two hours. After the whole has been cooled it is stirred into water, 14 parts of the following compound is obtained: ##STR246## It has a melting point of 112° to 114° C.

The compounds set out in Tables I and II may also be prepared according to the following Examples.

EXAMPLE 320

20.3 parts of p-ω-dichloropropiophenone, 33 parts of p-(diethylaminoethyloxyisopropylsulfonyl)-phenylhydrazine and 300 parts of methanol are stirred for five hours at 65° C. and then allowed to cool. 30 parts of 1-[p-(diethylaminoethyloxyisopropylsulfonyl)-phenyl]-3-[p-chlorophenyl]-.DELTA.² -pyrazoline is obtained. It has a melting point of 144° to 147° C.

p-(diethylaminoethyloxyisopropylsulfonyl)-phenylhydrazine may be prepared as follows:

35.8 parts of p-(diethylaminoethyloxyisopropylsulfonyl)-acetanilide, 80 parts of concentrated hydrochloric acid and 50 parts of water are stirred for sixty minutes at 90° to 100° C.

50 parts of ice is added. Diazotization is carried out at 0° to -5° C. with 7 parts of sodium nitrite dissolved in 15 parts of water. The diazonium salt solution is stirred at 0° to 5° C. into a solution of 65 parts of sodium sulfite and 280 parts of water. The whole is stirred for another hour. After cooling and adjusting the pH to 8 to 9 26 parts of p-(diethylaminoethyloxyisopropylsulfonyl)-phenylhydrazine is precipitated.

p-(diethylaminoethyloxyisopropylsulfonyl)-acetanilide is obtained in the following way:

2 parts of 50% caustic soda solution is dripped over two hours while stirring at 120° C. into 20 parts of p-allylsulfonylacetanilide and 25 parts of N,N-diethylethanolamine. The whole is stirred for another hour and then precipitation is effected with ice-water. 20 parts of p-(diethylaminoethyloxyisopropylsulfonyl)-acetanilide is obtained which does not crystallize well.

EXAMPLE 321

23.8 parts of 3,4-ω-trichloropropiophenone, 34.3 parts of p-(morpholinoethyloxyisopropylsulfonyl)-phenylhydrazine and 300 parts of methanol are stirred for five hours at 65° C. After cooling 1-[p-(morpholinoethyloxyisopropylsulfonyl)-phenyl]-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline is obtained. It has a melting point of 153° to 154° C.

EXAMPLE 322

1-[p-(dimethylaminoethyloxyisopropylsulfonyl)-phenyl]-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline having a melting point of 150° to 151° C. is obtained analogously to Example 321 using p-(dimethylaminoethyloxyisopropylsulfonyl)-phenylhydrazine.

EXAMPLE 323

1-[p-(dimethylaminopropyloxyisopropylsulfonyl)-phenyl]-3-(3',4'-dichlorophenyl)-Δ² -pyrazoline having a melting point of 140° to 142° C. is obtained analogously to Example 321 using p-(dimethylaminopropyloxyisopropylsulfonyl)-phenylhydrazine.

EXAMPLE 324

20.3 parts of p-ω-dichloropropiophenone, 30 parts of p-(morpholinoisopropylsulfonyl)-phenylhydrazine and 300 parts of methanol are stirred for five hours at 65° C. After cooling there is obtained 27 parts of 1- p-(morpholinoisopropylsulfonyl)-phenyl -3-(p-chlorophenyl)-Δ² -pyrazoline having a melting point of 157° to 169° C.

EXAMPLE 325

20.3 parts of p-ω-dichloropropiophenone, 28.5 parts of p-(butylaminoisopropylsulfonyl)-phenylhydrazine and 300 parts of methanol are stirred for five hours at 65° C. After cooling there is obtained 26 parts of 1-[p-(butylaminoisopropylsulfonyl)-phenyl]-3-(p-chlorophenyl)-Δ.sup.2 -pyrazoline having a melting point of 112° to 114° C.

The compounds shown in Table II are obtained by methods analogous to those described in the Examples.

    __________________________________________________________________________      ##STR247##                                                                                                                   Shade of                                                                 Dissolved                                                                            fluores-                        Ex.                                                                               R.sup.1                                                                           R.sup.2                                                                           R.sup.4 R.sup.5                                                                          R.sup.6                                                                           R.sup.7                                                                            X-A            in    cence                           __________________________________________________________________________     326                                                                               H  CH.sub.3                                                                          CH.sub.3                                                                               H H  Cl  OC.sub.2 H.sub.4N(CH.sub.3).sub.2                                                             dilute                                                                               blue                                                                     acid                                  327                                                                               H  H  C.sub.2 H.sub.5                                                                        Cl                                                                               H  H   OC.sub.3 H.sub.6N(CH.sub.3).sub.2                                                             "     greyish                                                                        blue                            328                                                                               H  CH.sub.3                                                                          C.sub.6 H.sub.5                                                                        Cl                                                                               CH.sub.3                                                                          Cl  OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     blue                            329                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     "                               330                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR248##    "     "                               331                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  NHC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                           "     "                               332                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR249##    "     "                               333                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR250##    "     "                               334                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR251##    "     "                               335                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  SO.sub.3 H     dilute                                                                               "                                                                        alkali                                336                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  NHC.sub.2 H.sub.4SO.sub.3 H                                                                   "     "                               337                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  OC.sub.2 H.sub.4 SO.sub.3 H                                                                   "     "                               338                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl  OC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2                                                     dilute                                                                               "                                                                        acid                                  339                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR252##    "     "                               340                                                                               H  H  H       Cl                                                                               CH.sub.3                                                                          Cl                                                                                  ##STR253##    "     "                               341                                                                               H  Cl H       Cl                                                                               H  Cl  OC.sub.2 H.sub.4N(CH.sub.3).sub.2                                                             "     "                               342                                                                               CH.sub.3                                                                          H  H       Cl                                                                               H  Cl                                                                                  ##STR254##    "     "                               343                                                                               CH.sub.3                                                                          H  H       Cl                                                                               H  Cl  OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                            "     greenish                                                                       blue                            344                                                                               CH.sub.3                                                                          Cl H       H H  OCH.sub.3                                                                          OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                            "     "                               345                                                                               CH.sub.3                                                                          Cl H       H H  CH.sub.3                                                                           OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     "                               346                                                                               H  H  H       Cl                                                                               H  Cl  OC.sub.3 H.sub.6 N(C.sub.3 H.sub.7).sub.2                                                     "     blue                            347                                                                               H  H  H       Cl                                                                               H  Cl  OC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2                                                     "     "                               348                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR255##    "     "                               349                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR256##    "     "                               350                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR257##    "     "                               351                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR258##    "     "                               352                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR259##    "     "                               353                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR260##    "     "                               354                                                                               H  H  H       Cl                                                                               H  Cl                                                                                  ##STR261##    "     "                               355                                                                               H  H  H       H H  H                                                                                   ##STR262##    "     greenish blue                   356                                                                               H  H  H       H H  CH.sub.3                                                                           OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     "                               357                                                                               H  H  H       H H  C.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     "                               358                                                                               H  H  C.sub.6 H.sub.4 CH.sub.3                                                               H H  Cl  OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                            "     blue                            359                                                                               H  H  C.sub.6 H.sub.4 OCH.sub.3                                                              H H  Cl  OC.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                            "     "                               360                                                                               H  H  C.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                      H H  Cl  OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                            "     "                               361                                                                               H  H  C.sub.6 H.sub.4 SO.sub.3 H                                                             H H  Cl  NHC.sub.4 H.sub.9                                                                             dilute                                                                               "                                                                        alkali                                362                                                                               H  H  C.sub.6 H.sub.4 SO.sub.3 H                                                             H H  Cl  NHC.sub.6 H.sub.13                                                                            "     "                               363                                                                               H  H  C.sub. 6 H.sub.4 SO.sub.3 H                                                            H H  Cl  NHC.sub.3 H.sub.7                                                                             "     "                               __________________________________________________________________________

example 364

37.6 parts of 1-[4'-(β,γ-epoxypropylsulfonyl)-phenyl-]3-p-chlorophenylpyrazoline, 41 parts of 3-dimethylaminopropylamine and 2 parts of diaminocyclo-[2,2,2]-octane are stirred in 80 parts of dimethylformamide for three hours at 130° to 140° C. The whole is allowed to cool, precipitated with water and suction filtered. There is obtained a yield of 29 parts (60.4% of theory) of the compound: ##STR263## The product is pale yellow and exhibits an intensely blue fluorescence in solution.

EXAMPLE 365

103.3 parts of the compound from Example B(c) and 27 parts of sodium carbonate are dissolved in 300 parts of water and 300 parts of N-methylpyrrolidone and heated for three hours at 70° to 80° C. 126 parts of sodium sulfite is then added and the whole is heated for another three hours at 70° to 80° C. The whole is cooled to ambient temperature, suction filtered, dried and 114 parts of the following compound is isolated: ##STR264## The product is pale yellow. A solution of the product in water has an intense blue fluorescence. NMR (D₆ -DMSO): OH-signal as a triplet at 4.46 ppm.

EXAMPLE 366

94 parts of the compound from Example A(c) and 24 parts of ethanolamine are heated in 300 parts of methanol for five hours at 60° to 65° C. The whole is cooled to 0° to 5° C. and 86 parts of the following compound is isolated by suction filtration: ##STR265## The melting point is 106° to 110° C.

The product is pale yellow and its solution in dimethylformamide has an intense blue fluorescence. (Absorption λ_(max). 368 nm, Reflectance λ_(max). 437.5 nm).

Compounds set out in the following Table are obtained analogously to Example 366:

    __________________________________________________________________________      ##STR266##                                                                                                 Fluorescence in                                   Ex. R.sub.5                                                                            R.sub.6                                                                             XA        m.pt. dimethylformamide                                 __________________________________________________________________________     367 H   H    NHC.sub.4 H.sub.9                                                                        109-114                                                                              blue                                              368 Cl  H    SO.sub.3 Na                                                                              >300  greenish blue                                     369 Cl  H    NH(CH.sub.2).sub.3 N(CH.sub.3).sub.2                                                     125-128                                                                              greenish blue                                     370 Cl  CH.sub.3                                                                             ##STR267##                                                                              195-200                                                                              greenish blue                                     371 H   H                                                                                    ##STR268##                                                                              205-210                                                                              blue                                              372 H   H    OCH.sub.3 120-125                                                                              blue                                              __________________________________________________________________________ 

We claim:
 1. A compound which in the form of the free acid corresponds to the formula ##STR269## in which B³ is hydrogen or C₁ to C₄ alkyl,R², r³, r⁵, r⁶ and R⁷ are independently hydrogen, chlorine, bromine, fluorine, methyl, ethyl, methoxy or ethoxy and R⁴ is hydrogen, C₁ to C₄ alkyl, benzyl, phenylethyl, phenyl or phenyl substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy, cyano or hydroxysulfonyl.
 2. A compound according to claim 1 in which R², R³, R⁴, R⁵, R⁶ and B³ are hydrogen.
 3. A compound according to claim 2 in which R⁷ is chlorine. 